Crosslinked fluoroaliphatic coating composition having oxazoline or oxazine moieties and integrated colloidal silica

ABSTRACT

Coatings prepared from water-based compositions comprise an aqueous solution, emulsion, or dispersion of (a) a water-soluble or water-dispersible polymer or oligomer having at least one anionic moiety which is capable of reacting with an oxazoline or oxazine moiety; (b) a water-soluble or water-dispersible polymer or oligomer having at least one oxazoline or oxazine moiety; and (c) colloidal silica; at least one of the components (a) and (b) further comprising at least one fluoroaliphatic moiety. The coatings have low surface energy and high abrasion resistance.

This application is a divisional of 08/752,275 filed Nov. 20, 1996, nowU.S. Pat. No. 6,005,043 which is a continuation-in-part of applicationNo. 08/494,157 filed Jun. 23, 1995 now U.S. Pat. No. 5,608,003.

FIELD OF THE INVENTION

This invention relates to water-based, one-part, shelf-stable coatingcompositions made from organic and inorganic materials. The organicmaterials contain fluorine and offer low surface energy properties. Theaddition of inorganic materials such as colloidal silica providesabrasion-resistant coatings without adversely affecting the low surfaceenergy properties.

BACKGROUND OF THE INVENTION

Water-based, cross-linkable, fluorochemical low surface energy coatingsystems made from polymeric surfactants and oxazoline polymercrosslinkers have been described in U.S. Pat. Nos. 5,382,639, 5,294,662,5,006,624, and 4,764,564.

The present invention has filled a void in providing a low surfaceenergy hard coating system with excellent abrasion resistance. This voidhas been filled by providing a coating system which integrates afluorine-containing, crosslinked organic polymeric surfactant withcolloidal silica.

SUMMARY OF THE INVENTION

Accordingly, the present invention is a water-based compositioncomprising an aqueous solution, emulsion, or dispersion of: (a) awater-soluble or water-dispersible polymer or oligomer having at leastone anionic moiety which is capable of reacting with an oxazoline oroxazine moiety; (b) a water-soluble or water-dispersible polymer oroligomer having at least one oxazoline or oxazine moiety; and (c)colloidal silica. At least one of polymers or oligomers (a) and (b) hasat least one fluoroaliphatic moiety, and either polymer or oligomer (a)or (b) (or both) can further contain at least one silyl moiety.Preferably, the fluorine content of the composition is at least about 10weight percent.

Thus, for example, an especially preferred embodiment in a water-basedcomposition includes an aqueous solution, emulsion, or dispersion of

(a) a water-soluble or water-dispersible polymer or oligomer havinginterpolymerized units derived from at least one fluoroaliphatic-radicalcontaining acrylate, at least one carboxy-containing monomer, and atleast one silyl moiety derived from a trialkoxysilylalkyl acrylate ormethacrylate or trialkoxysilylalkyl mercaptan in which alkyl has from 1to about 10 carbon atoms and alkoxy has from 1 to about 3 carbon atoms;

(b) a water-soluble or water-dispersible polymer or oligomer having atleast one oxazoline or oxazine moiety; and

(c) colloidal silica having an average particle diameter of at leastabout 5 nanometers.

A second aspect of the invention is a coating comprising the curedcomposition, which comprises crosslinked polymer (e.g., containing atleast one amide-ester crosslink moiety derived from the reaction ofcarboxyl groups with oxazoline or oxazine moieties) having colloidalsilica integrated therein.

A third aspect of the present invention is a coated article comprisingthe coating.

The coating compositions can be used to provide a low surface energyhard coat to protect smooth, flat surfaces of essentially any kind(e.g., poly(vinyl chloride), polycarbonate, polyester, nylon, metals(either painted or bare), glass, wood, stone, etc.). The good abrasionresistance properties will protect such surfaces from physical damage,and the low surface energy properties will provide easily cleanable andpossibly antigraffiti properties. The coating can also be used as a lowadhesion backsize for adhesives.

The significant difference of the present invention over relatedtechnologies is the incorporation of colloidal silica into the coatingcomposition. The previous organic polymer-based coating systems havebeen transformed into organic-inorganic composite compositions. Thefinished coatings therefore become much more abrasion-resistant and aremore durable in protective applications. Unexpectedly, the antigraffitiand release properties of the coating systems are also not degradeddespite the incorporation of the high surface energy, hydrophilic,colloidal silica, even with compositions containing a lower weightpercentage of fluorine in many cases.

DETAILED DESCRIPTION OF THE INVENTION

As used herein “anionic” means capable of forming anions in aqueousmedia. As used herein, “copolymers” or “polymers” includes polymers andoligomers.

The anionic moiety-containing polymers useful in this inventionpreferably have an average of more than two reactive ionic moieties perpolymer. Preferably, the anionic moiety-containing polymers have anaverage of more than one fluoroaliphatic moiety per polymer. Suchpolymers include those described, for example, in U.S. Pat. Nos.5,382,639, 5,294,662, 5,006,624 and 4,764,564 supra, which descriptionsare incorporated herein by reference.

Useful anionic moieties include carboxy and mercaptan moieties, whichcan be reacted with bases to obtain carboxylate and mercaptide salts. Atlower pH values, these moieties become essentially nonionic. Theparticularly preferred anionic moiety is carboxylate. The carboxylateanionic polymer can be utilized in the water-based compositions of thisinvention as its ammonium salts.

The anionic moiety-containing polymers, polymer component, orsurfactant, useful in the present invention, can be prepared, forexample, by the addition polymerization of one or more ethylenicallyunsaturated carboxy-containing monomers (e.g., acrylic acid, methacrylicacid, and esters thereof such as 2-carboxyethyl acrylate) with one ormore ethylenically unsaturated comonomers (e.g., acrylic esters, vinylethers, or styrenic monomers). The comonomers can be further substitutedwith fluorine. The carboxy-containing monomer is preferably acrylic acid(due to stability considerations) or 2-carboxyethyl acrylate (due tocrosslinking considerations). Preferably, the anionic moiety-containingpolymers further contain a fluoroaliphatic radical-containing,ethylenically unsaturated monomer, such as perfluoroalkyl acrylateesters, e.g., CH₂═CHCOOCH₂CH₂N(Et)SO₂C₈F₁₇, or fluoroalkyl vinyl ethers,e.g., CH₂═CHOCH₂C₇F₁₅, which can be incorporated into the anionicmoiety-containing polymer by addition polymerization.

The oxazine or oxazoline polymers or oligomers useful in the presentinvention can be prepared by the addition polymerization of anoxazine-or oxazoline-containing ethylenically unsaturated monomer, suchas 2-isopropenyl-2-oxazoline (IPO) and those represented by the generalstructures:

wherein R₁ is an unsaturated organic radical capable of additionpolymerization, such as 1,2-ethylenic unsaturation. Preferably, R₁ is anisopropenyl group. Each R₂ is independently hydrogen, halogen, or asubstituted organic radical, preferably R₂ is hydrogen. Optionally analiphatic or fluoroaliphatic radical-containing, ethylenicallyunsaturated monomer, such as acrylate esters, e.g.,CH₂═CHCO₂CH₂CH₂N(Et)SO₂C₈F₁₇, vinyl ether, or styrenic monomers can becopolymerized with the oxazine- or oxazoline-containing ethylenicallyunsaturated monomer.

The oxazoline- or oxazine-containing polymers useful in the presentinvention preferably have an average of more than two oxazoline oroxazine moieties per polymer. If desired, aziridine group-containingoligomers can be utilized in place of the oxazoline- oroxazine-containing polymers or oligomers, provided that shelf stabilityor one-part formulation is not required.

The aliphatic moiety of the aliphatic radical-containing monomer, ifpresent, can be a monovalent aliphatic or alicyclic moiety, preferablysaturated. It can be linear, branched, cyclic, or combinations thereof.It can contain catenary, i.e., in-chain, heteroatoms bonded only tocarbon atoms, such as oxygen, divalent or hexavalent sulfur, ornitrogen. The aliphatic moiety has from 1 to about 20 carbon atoms,preferably from 1 to about 10 carbon atoms.

The fluoroaliphatic moiety of the fluoroaliphatic radical-containingmonomer, if present, can be a fluorinated, stable, inert, preferablysaturated, non-polar, monovalent aliphatic or alicyclic moiety. It canbe straight chain, branched chain, cyclic, or combinations thereof. Itcan contain catenary heteroatoms, bonded only to carbon atoms, such asoxygen, divalent or hexavalent sulfur, or nitrogen. A fully-fluorinatedmoiety is preferred but hydrogen or chlorine atoms can be present assubstituents, provided that not more than one atom of either is presentfor every two carbon atoms. The moiety has at least about 3 carbonatoms, preferably from about 3 to about 20 carbon atoms, and mostpreferably from about 4 to about carbon atoms. The terminal portion ofthe moiety is a perfluorinated moiety which preferably contains at least7 fluorine atoms, e.g., CF₃CF₂CF₂—, (CF₃)₂CF—, F₅SCF₂—, or the like.

The polymers useful in this invention, i.e., those having at least oneanionic moiety (the surfactant component), or those having at least oneoxazoline or oxazine moiety (the cross-linking component), canoptionally contain at least one silyl moiety. The silyl moiety can beformed on one or both of the polymers by a compound which can berepresented by the formula

X—R—Si(OR′)₃

wherein X is a group reactive to radical polymerization, such as anunsaturated acrylate or methacrylate radical or a mercapto group; R isalkylene of 1 to about 10 carbon atoms; and R′ is alkyl of 1 to about 3carbon atoms.

The silyl moiety can be incorporated either in the polymer chain, using,for example, a trialkoxysilylalkyl acrylate or methacrylate, or at theterminal end of the polymer chain via a chain transfer agent, using, forexample, a trialkoxysilylalkyl mercaptan, preferablymercaptopropyltrimethoxysilane (MPTS). The silane content of theresulting polymer can vary up to a level where significant silanecoupling occurs, resulting in destabilization of the composition. Forexample, the amount can range from about 0.1 to about 15 weight % basedon the weight of the total monomer feed. Preferably, the silyl moiety isattached to the surfactant component, the anionic moiety-containingpolymer.

Other functional groups can optionally be incorporated into thesurfactant or cross-linking polymer components, such as polymerizableultraviolet (UV) absorbers, e.g., NORBLOC™ 7966(2-(2′-)hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole),available from Noramco Inc.

Aqueous colloidal silica dispersions (silica hydrosols) are availablecommercially with different particle sizes (average particle diameters)and can be used in preparing the compositions of the invention. Theuseful particle size for the present invention generally ranges fromabout 1 nanometer to about 1 micrometer, preferably, at least about 5nanometers (nm), more preferably from about 20 to about 75 nm. The useof particles larger than 75 nm may result in the crosslinked coatingbecoming translucent or even opaque, in contrast to the use of particlesizes in the preferred range which result typically in transparentcoatings. The use of larger particle sizes however will not diminish thelow surface energy properties of the coating, and will impart improvedabrasion resistance. Particle sizes of less than about 5 nm can degradethe low surface energy properties at relatively low loading levels dueto the large surface area for a given added weight of colloidal silica.

The commercially available colloidal silica hydrosols generally containfrom about 15 to about 50 weight % silica. Most are stabilized byalkali, e.g., sodium, potassium, or ammonium hydroxides. Examples ofsols which have been found useful include: Nalco™ 2327 and Nalco™ 2329silica hydrosols, having colloidal silica particle sizes of about 20 and75 nm respectively and a concentration of 40 weight percent silica inwater, available from Nalco Chemical Company of Oakbrook, Ill. Both aresuspended in alkaline aqueous media. Another useful dispersion is LUDOX™AS-40 silica hydrosol, which uses ammonium as a stabilizing counterion,having a particle size of about 22 nm and a concentration of 40 weight %silica in water, available from E. I. duPont de Nemours of Wilmington,Del.

Other inorganic oxides (e.g., colloidal titania, colloidal alumina,colloidal zirconia, colloidal vanadia, colloidal chromia, colloidal ironoxide, colloidal antimony oxide, colloidal tin oxide, colloidalalumina-coated silica, and mixtures thereof) can also be utilized in thecompositions of the invention (either alone or in combination withsilica), provided that they can form stable dispersions with thepolymeric components of the compositions.

The surfactant polymer component, crosslinking polymer component, andsilica hydrosol can be combined in any order and manner of combinationby direct mixing using any conventional means such as mechanicalagitation, ultrasonic agitation, stirring, and the like. For example,silica hydrosol can be added to the combined polymer formulation, i.e.,a mixture of the surfactant polymer component and the crosslinkingpolymer component, or prior to formulation to either the surfactantpolymer component or the crosslinking polymer component. Preferably, thecrosslinking component and/or the surfactant component are added to thesilica hydrosol while maintaining the pH of the mixture at valuesgreater than 8 to avoid precipitation of one or more of the components.

Silica hydrosol can be added in an amount sufficient to impart thedegree of abrasion resistance desired for a particular application,while maintaining the desired surface energy characteristics.Preferably, the coating formulation contains from about 5 to about 70weight percent silica. At high weight percentages, for example, fromabout 50 to about 70 weight %, or with very fine particle sizes, forexample, less than about 5 nm, the abrasion resistance of the resultingcoating is improved, but the low energy surface properties may bereduced compared with a coating containing no silica. More preferably,silica is added in amounts of from about 15 to about 50 weight percent;most preferably, from about 15 to about 40 weight percent.

The coating composition can contain additional components such asfillers. Thus, for example, should transparency of the coating not be arequirement, e.g., in paints, etc., the composition can contain dyes;inorganic, non-colloidal fillers such as tin oxide, titanium dioxide,alumina, or alumina-coated silica; non-colloidal silica (e.g., fumedsilica); carbon black; and/or organic fillers.

The coating composition can be cured at elevated and room temperatures,e.g., from about 20 to about 125° C. The use of elevated temperatures,e.g., 50° C. to 125° C., results in faster cure and is preferred.

The cured coatings are transparent, translucent, or opaque, depending onthe colloidal silica particle size and whether additional componentssuch as fillers have been incorporated. The cured coatings are resistantto solvents and water, and have excellent abrasion resistance withoutsacrificing their very low surface energy (10-15 dynes/cm) properties.

The coating compositions of this invention can be applied to a widevariety of substrates to impart abrasion resistance, solvent resistance,and corrosion resistance, as well as to impart release characteristicsto the surface. In general, the type of substrates that can be coated inaccordance with this invention include rigid and flexible substratessuch as: plastics, glass, metal, and ceramics. For example, softsubstrates such as plastics can be rendered abrasion resistant and marresistant by the practice of this invention. Representative examplesinclude: lenses used in ophthalmic spectacles, sunglasses, opticalinstruments, illuminators, watch crystals, and the like; plastic windowglazing; signs and decorative surfaces such as wallpaper and vinylflooring. Metal surfaces can be rendered resistant to corrosion by thepractice of this invention, whereby the brilliance of polish can bemaintained on decorative metal strips and mirrors. Further, the coatingcompositions can be colored by addition of dyes and pigments and appliedto surfaces as a paint.

In addition, the coating composition can be applied as a protectivecoating on aircraft (in de-icing wings), as automotive polish, asautomotive topcoat, and as automotive transit coating; can be used oncarpet, concrete, fishing line, formica, medical surfaces, siding,sinks, showers, textiles, vinyl flooring, and wallcovering; and can beused in food release, mold release, adhesive release, and the like.

The coating compositions of this invention can be applied to a substrateusing any conventional technique. For example, the composition can bebrushed or sprayed (e.g., as an aerosol) onto a substrate, or thesubstrate can be immersed in the coating composition or can bespin-coated. When coating flat substrates, it is preferable to knife- orbar-coat the substrate to ensure uniform coatings.

The coating compositions of the present invention can be applied to asubstrate in any desired thickness. It has been found that coatings asthin as a few microns offer excellent abrasion resistance and lowsurface energy. However, thicker coatings (e.g., up to about 20 micronsor more) can be obtained by applying a single thicker coating or byapplying successive layers of the coating to the substrate. The lattercan be done by applying a layer of the coating composition to thesubstrate and then drying without extensive curing, for example, byheating the coated substrate for about one minute at about 75° C.Successive layers of the coating can then be applied to dried, butuncured, coatings. This procedure can be repeated until the desiredcoating thickness is obtained.

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention. In the examples,all temperatures are in degrees Centigrade and all parts and percentagesare by weight unless indicated otherwise.

EXAMPLES

In the following examples and comparative examples (controls), theprecursor polymers such as for example the surfactant component polymerand the crosslinking component polymer were prepared essentially asdescribed in U.S. Pat. Nos. 5,382,639, 5,294,662, 5,006,624, and4,764,564 cited above. The coating compositions were prepared, appliedto a polyethylene terephthalate film substrate, cured, and evaluated forlow surface energy properties and abrasion resistance performance. Theresults are shown in Tables 1 and 2, and the test methods utilized aredescribed below:

The “pen test” described in U.S. Pat. No. 5,294,662 was used. The testinvolved drawing a fine line on a coated film using a black Sharpie™fine point permanent marker available from the Sanford Company. A numbervalue of 0 to 3 was assigned based on the appearance of the resultingline. The values were defined as follows: 3: totally unwettable, inkdewets to form a discontinuous line (best); 2: ink partially dewets toform a very thin continuous line; 1: some dewetting; 0: totallywettable, same as non-treated surface (worst). For illustration of themethod, a line written on a polytetrafluoroethylene surface dewetsslightly and is assigned a 1.

The abrasion resistance of the coatings was determined by measuring theresulting % haze of a film sample using ASTM D-1044-90 on a TeledyneTabor Abrasor with a 500 g load and a pair of CS-10F Calibrasers. Thelower the resulting percent haze, the higher the abrasion resistance ofthe coating.

The resulting coatings were also tested for water contact angle byessentially the method described by Zisman, W. A., in “Contact Angle,Wettability, and Adhesion,” Advances in Chemistry, Series 43, AmericanChemical Society, Washington, D.C. (1964). An ESCA test comprisedevaluating the samples for surface fluorine content using a ¼ inch by ¼inch portion of the coated sample using a Fison F Inspector™ ESCAanalyzer. The sample was scanned from 0 electron volts to 1100 electronvolts, and the results were averaged for four scans.

Comparative Example 1

To a 5 L 3-necked flask equipped with a mechanical stirrer, a coolingcondenser, and a temperature control device was added2-(N-ethylperfluorooctanesulfonamido)ethyl acrylate (600 g, available asFX-13™ acrylate from the 3M Company), 2-carboxyethyl acrylate (400 g),azobis-isobutyrylnitrile (AIBN, 6.0 g), N-methylpyrrolidinone (400 g),and isopropanol (600 g). The solution was purged with nitrogen for about3 min. and heated to initiate polymerization. As the reaction becameexothermic the temperature control was adjusted to 70° C. and heatingcontinued at that temperature for about 2.5 hours. The cooling condenserwas replaced by a distillation condenser, and isopropanol was distilledfrom the reaction mixture. The resulting polymer was neutralized byaddition of aqueous ammonia and water until the solution was basic.

To 30 g of the above acrylate copolymer solution (8.1 g solids, 22.5mmoles of carboxylic groups) was added an aqueous solution ofisopropenyl oxazoline/ethyl acrylate/methyl methacrylate terpolymer(85/5/10, 3.2 g solids, 24.8 mmoles of oxazoline groups, available fromNippon Shokubai Co., Ltd. as CX-WS-300™ crosslinker) followed by 2.5 gof N-methyl pyrrolidinone. The pH of the resulting solution was adjustedto 7.5-8 by adding aqueous ammonia. This formulation is hereinafterreferred to as “WXF Formulation” (Waterborne CrosslinkableFluorochemical coating system).

This WXF Formulation was allowed to sit at room temperature for about1-2 days after which it was then coated onto a primed polyethyleneterephthalate film with a #30 Mayer rod to a coating thickness of about10-12 microns. The resulting coating was then heated in a oven at 120°C. for 30 min. The finished film was transparent and resistant tosolvents and water.

The fluorine percentage of this composition was calculated as 22% fromthe known fluorine content of the monomers. The resulting film wasevaluated using the described “pen test”. The results are shown in Table1.

Example 1

To colloidal silica (40 g solids, Ludox™ AS-40 hydrosol available fromDuPont, 22 nm average particle diameter), was added concentrated aqueousammonia (about 0.5 g), water (80 g), N-methylpyrrolidinone (26 g), andthe CX-WS-300υ crosslinker described in Comparative Example 1 (5.2 gsolids) with stirring. A translucent solution (17.5% solids) wasobtained.

To the CX-WS-300™ crosslinker/SiO₂ solution described above (1.75 gsolids, 1.55 g SiO₂) was added under vigorous stirring a solution of“WXF Formulation” (1.75 g solids) described in Comparative Example 1 toproduce a translucent solution (17.5% solids, 44% SiO₂ by solids). Thissilica containing formulation was then coated, cured, and evaluatedessentially as described in Comparative Example 1. The results of thetests are shown in Table 1.

Example 2

As in Example 1, “WXF Formulation” (3.1 g solids) was added to thetranslucent solution containing colloidal silica, CX-WS-300™crosslinker, and N-methylpyrrolidinone (1.75 g solids, 1.55 g SiO₂) toproduce a milky solution (17.5% solids, 32% SiO₂ by solids). This silicacontaining formulation was then coated, cured, and evaluated essentiallyas described in Comparative Example 1. The results of the tests areshown in Table 1.

Example 3

As in Example 1, “WXF Formulation” (6.7 solids) was added to thetranslucent solution containing colloidal silica, CX-WS-30™ crosslinker,and N-methylpyrrolidinone (1.75 g solids) to produce a translucentsolution (17.5% solids, 18.4% SiO₂ by solids). This silica containingformulation was then coated, cured, and evaluated essentially asdescribed in Example 1. The results of the tests are shown in Table 1.

Comparative Example 2

To a 1 L 3-necked flask equipped with a mechanical stirrer, a condenser,and a temperature control device was added2-(N-ethylperfluorooctanesulfonamido)ethyl acrylate (120 g, available asFX-13™ acrylate from the 3M Company), 2-carboxyethyl acrylate (80 g,),mercaptopropyltrimethoxysilane (MPTS, 4.0 g, Aldrich), AIBN (1.2 g),N-methylpyrrolidinone (100 g), and isopropanol (100 g). The solution waspurged with nitrogen for about 3 min. and heated to initiate thepolymerization. As the reaction became exothermic the temperaturecontrol was adjusted to 70° C. and heating continued at that temperaturefor about 3 hours. The isopropanol was removed under reduced pressureand the resulting polymer was neutralized by addition of aqueous ammoniaand water until the solution was basic.

To 40 g of the above acrylate terpolymer solution (12.0 g solids, 32.7mmoles of carboxylic groups) was added CX-WS-300™ crosslinker (4.7 gsolids, 3.6 mmoles of oxazoline groups), followed by 5.7 g of N-methylpyrrolidinone. The pH of the solution was adjusted to 7.5-8 by addingaqueous ammonia. This formulation is referred to hereinafter as “WXF/2%MPTS Formulation” (Waterborne Crosslinkable Fluorochemical coatingsystems with mercaptopropyltrimethoxysilane incorporated in thepolymeric chain). This formulation was evaluated essentially asdescribed in Comparative Example 1. The test results are shown in Table1.

Example 4

The “WXF/2% MPTS Formulation” described in Comparative Example 2 (1.75 gsolids) was added to a translucent solution containing colloidal silica,CX-WS-300™ crosslinker, and N-methylpyrrolidinone (1.75 g solids) toproduce a translucent solution (17.5% solids, 44% SiO₂ by solids). Thissilica containing formulation was then coated, cured, and evaluatedessentially as described in Comparative Example 1. The results of thetests are shown in Table 1.

Example 5

As in Example 4, “WXF/2% MPTS Formulation” (3.1 g solids) was added to atranslucent solution containing colloidal silica, CX-WS-300™crosslinker, and N-methylpyrrolidinone (1.75 g solids) to produce atranslucent solution (17.5% solids, 32% SiO₂ by solids). This silicacontaining formulation was then coated, cured, and evaluated essentiallyas described in Comparative Example 1. The results of the tests areshown in Table 1.

Example 6

As in Example 4, “WXF/2% MPTS Formulation” (6.7 g solids) was added to atranslucent solution containing colloidal silica, CX-WS-300™crosslinker, and N-methylpyrrolidinone (1.75 g solids) to produce atranslucent solution (17.5% solids, 18.4% SiO₂ by solids). Thissilica-containing formulation was then coated, cured, and evaluatedessentially as described in Comparative Example 1. The results of thetests are shown in Table 1.

Comparative Example 3

An aqueous solution of 2-(N-ethylperfluorooctanesulfonamido)ethylacrylate (FX-13™ acrylate) and 2-isopropenyl-2-oxazoline (“IPO”)copolymer (20/80 weight ratio, 1.9 g solids, 13.7 mmoles of oxazolinegroups) prepared essentially according to the method described in U.S.Pat. No. 5,294,662) was mixed with an aqueous solution of FX-13™acrylate/CEA copolymer (60/40 weight ratio, see Comparative Example 1for preparation, 4.1 g solids, 11.3 mmoles of carboxylic acid groups),followed by addition of 2.9 g of N-methylpyrrolidinone and 26.3 g ofwater. The resulting solution (10% solids) was clear. This formulationwas then coated, cured, and evaluated essentially as described inComparative Example 1. The test results are shown in Table 1.

Example 7

To colloidal silica (Ludox™ AS-40 hydrosol, 1.0 g solids) was graduallyadded, under stirring, the formulation described in Comparative Example3 (3.0 g of solids) to produce a translucent silica containingformulation (12.3% solids, 25% SiO₂ by solids). This formulation wasthen coated, cured, and evaluated essentially as described inComparative Example 1. The results of the tests are shown in Table 1.

Comparative Example 4

To a 500 mL 3-necked flask equipped with a mechanical stirrer, acondenser, and a temperature control device was addedCH₂═CHCOOCH₂CH₂C₈F₁₇ (54 g, available as Zonyl™ acrylate from DuPont),2-carboxyethyl acrylate (36 g), AIBN (0.54 g),mercaptopropyltrimethoxysilane (1.8 g), N-methylpyrrolidinone (45 g),and isopropanol (45 g). The resulting solution was purged with nitrogenand heated to initiate polymerization. As the reaction became exothermicthe temperature control was adjusted to 70° C. and heating continued atthat temperature for about 3.5 hours. Isopropanol was removed underreduced pressure, and the resulting polymer was neutralized by additionof aqueous ammonia until the solution was basic. Part of this solution(12.9 g solids, 35 mmoles of carboxylic groups) was further mixed withCX-WS-300™ crosslinker (4.6 g solids, 35 mmoles of oxazoline group) toproduce a clear coating formulation. This formulation was then coated,cured, and evaluated essentially as described in Comparative Example 1.The results of the tests are shown in Table 1.

Example 8

To colloidal silica (Ludox™ AS-40 hydrosol, 2 g solids) was added 3drops of concentrated ammonia, 5 g of water, the coating formulation ofComparative Example 4 (5.7 g solids), and CX-WS-300™ crosslinker (0.26 gsolids) with stirring to produce a silica-containing formulation (16.5%solids, 25% SiO₂ by solids). This formulation was then coated, cured,and evaluated essentially as described in Comparative Example 1. Theresults of the tests are shown in Table 1.

Comparative Example 5

To a 500 mL 3-necked flask equipped with a mechanical stirrer, acondenser, and a temperature control device was added2-(N-methylperfluorobutanesulfonamido)ethyl acrylate (30 g),2-carboxyethyl acrylate (20 g), AIBN (0.3 g), N-methylpyrrolidinone (20g), and isopropanol (30 g). The solution was purged with nitrogen forabout 3 min. and heated to initiate the polymerization at 70° C. for 4hours. Isopropanol was removed under reduced pressure, and the resultingpolymer was neutralized by addition of aqueous ammonia until thesolution was basic. Part of this solution (12.5 g solids, 35 mmoles ofcarboxylic groups) was further mixed with CX-WS-300™ crosslinker, (4.5 gsolids, 35 mmoles of oxazoline group) to produce a clear coatingformulation. This formulation was aged at 65° C. for 5 hours and thencoated, cured, and evaluated essentially as described in ComparativeExample 1. The results of the tests are shown in Table 1.

Example 9

To colloidal silica (Ludox™ AS-40 hydrosol, 2 g solids) was added 3drops of concentrated ammonia, water (4.7 g), and N-methylpyrrolidinone(0.6 g), followed by the addition of the formulation prepared inComparative Example 5 (5.74 g solids) and CX-WS-300™ crosslinker (0.26 gsolids) under stirring to produce a silica containing formulation (17.5%solids, 25% SiO2 by solids). This formulation was then coated, cured,and evaluated essentially as described in Comparative Example 1. Theresults of the tests are shown in Table 1.

Comparative Example 6

To a 1 L 3-necked flask equipped with a mechanical stirrer, a condenser,and a temperature control device was added2-(N-ethylperfluorooctanesulfonamido)ethyl acrylate (70 g), methacrylicacid (30 g), AIBN (0.6 g), N-methylpyrrolidinone (40 g), and isopropanol(60 g). The solution was purged with nitrogen for about 3 min. andheated at 65° C. for 5 hours to initiate the polymerization.N-methylpyrrolidinone (10 g) was added after the polymerization.Isopropanol was removed under reduced pressure, and the resultingpolymer was neutralized by addition of aqueous ammonia until thesolution was basic. Part of this solution (12.7% solids, 44.3 mmoles ofcarboxylic groups) was further mixed with the CX-WS-300™ crosslinker(8.4 g solids, 64 mmoles of oxazoline groups) and N-methylpyrrolidinone(13.8 g) to produce a clear coating formulation. This formulation wasaged at 65° C. for 5 hours and then coated, cured, and evaluatedessentially as described in Comparative Example 1. The results of thetests are shown in Table 1.

Example 10

To colloidal silica (Ludox™ AS-40 hydrosol, 3.8 g solids) was added 3drops of concentrated ammonia and water (9 g), followed by the additionof the formulation prepared in Comparative Example 6 (10.5 g) solids)with stirring to produce a silica containing formulation (11.8% solids,25.5% SiO₂ by solids). This formulation was then coated, cured, andevaluated essentially as described in Comparative Example 1. The resultsof the tests are shown in Table 1.

TABLE 1 Water Haze %, ESCA Contact Wt. % 200 C/F/Si Pen Angle Sample Wt.% F SiO₂ Cycles Coating Components (%) Test (degrees) Comparative 22.2 020 WXF Formulation 49/28/0   3 100 Example 1 Example 1 11.1 44 5.9 WXFFormulation + SiO₂ 39/21/7.8 0 136 Example 2 14.2 32 9.8 WXFFormulation + SiO₂ 46/26/1.8 3 102 Example 3 17.6 18.4 13 WXFFormulation + SiO₂ 46/28/0.6 3 104 Comparative 21.8 0 21 WXF/2% MPTSFormulation 48/26/0   3 103 Example 2 Example 4 10.5 44 8.6 WXF/2% MPTSFormulation + SiO₂ 43/25/4.0 1 119 Example 5 14.0 32 10 WXF/2% MPTSFormulation + SiO₂ 44/28/1.8 3 106 Example 6 17.5 18.4 13 WXF/2% MPTSFormulation + SiO₂ 47/27/0.7 3 104 Comparative 24.5 0 22WXF/FX-13/PIPO(20/80) 48/26/1.4 3  94 Example 3 Example 7 18.4 25 10WXF/FX-13/PIPO(20/80) + SiO₂ 46/26/1.5 3 100 Comparative 27.1 0 35WXF/2% MPTS & Zonyl 47/33/0   3 108 Example 4 Acrylate Example 8 19.3 2510 WXF/2% MPTS & Zonyl Acrylate + SiO₂ 46/32/1.1 3 110 Comparative 18.30 9.5 WXF/MeFBSEA 49/22/0   3  98 Example 5 Example 9 13.1 25 7.0WXF/MeFBSEA + SiO₂ 46/32/1.1 3 102 Comparative 21.8 0 16.8 WXF/MAA47/32/0   3 103 Example 6 Example 10 16.2 25.5 9.2 WXF MAA + SiO₂46/31/0.7 3 106

The data in Table 1 shows that the abrasion resistance of thecrosslinked coatings was significantly improved and the low surfaceenergy essentially unaffected after the incorporation of silica. Whereasthe percentage of haze for Comparative Example 1 (without silica) is 20%after 200 cycles, Example 2 (with 32% silica based on total solids) isonly 9.8%. Neither the water contact angle (100 vs. 102) nor the pentest results (3 vs. 3) was substantially affected by addition ofcolloidal silica, even though Comparative Example 1 has a much higherfluorine level (22.2%) than that of Example 2 (14.2%). The ESCA analysesshow that the surface of the coatings has much higher fluorine contentand much lower silica content than would be expected when compared tothe bulk calculated values. Furthermore, the abrasion resistance of thecrosslinked coatings was in proportion to the silica level in the finalcomposition (Examples 1-6).

Example 11

A sample of colloidal silica (Ludox™ TM-50 hydrosol, 12 g solids) wasdiluted with water to 60 g total, followed by addition of concentratedammonia to adjust the pH to about 9. To “WXF/2% MPTS Formulation” (34.4g solids) was added CX-WS-300™ crosslinker (1.6 g solids), followed byN-methylpyrrolidinone (1.7 g), and water (6.0 g). The two solutions werethen combined to produce a final coating formulation with 25% SiO₂. Thesample was then coated and evaluated essentially as described inComparative Example 1. The test results are shown in Table 2.

Examples 12-14

All the samples in this group were prepared using the materials andessentially the procedures described in Example 11, but the type ofcolloidal silica was varied as shown in Table 2. The samples were thencoated and evaluated essentially as described in Comparative Example 1.The test results are shown in Table 2.

TABLE 2 Water Haze %, ESCA Contact Wt. % Wt. % 200 C/F/Si Pen AngleSample F SiO₂ Cycles Type of Colloidal Silica (%) Test (degrees) Example15.6 25 11.4 Ludox ™ TM-50 hydrosol, 46/26/1.0 3 102 11 particle size:22 nm Example 17.2 18.4 11.6 Ludox ™ SM-30 hydrosol, 45/26/1.9 1 108 12particle size: 7 nm Examp1e 16.7 25 7.3 Nalco ™ 2329 hydrosol, 50/25/0  3 106 13 particle size: 75 nm Examp1e 13.3 40 4.2 Nalco ™ 2329 hydrosol,49/27/0.8 3 105 14 particle size: 75 nm

The data in Table 2 indicates that different brands and particle sizesof colloidal silica can be used to improve abrasion resistance of thecoatings, relative to a coating that contains no colloidal silica, andstill maintain low surface energy properties.

Examples 15-24

In Examples 15-24, “WXF/2% MPTS Formulation” (described above inComparative Example 2) was utilized, along with the various differenttypes of colloidal silica shown in Table 3 below. The resultingcompositions were coated with a #15 Meyer bar onto clear PET film andwere cured at 120° C. for 15 minutes. The resulting coatings were thenevaluated using the above-described “pen test”. The results are shown inTable 3.

Example 15

To colloidal silica (Ludox™ SM-30 hydrosol available from Du Pont, 6.0g, 1.8 g solids) was added concentrated ammonia (1.0 g) and water (26.5g), followed by addition of “WXF/2% MPTS Formulation” (21 g, 4.2 gsolids) with stirring. The resulting composition was quite clear(composition solids: 11%; SiO₂ wt % based on total dry solids: 30%).

Example 16

To the composition of Example 15 (20 g) was added “WXF/2% MPTSFormulation” (22 g) to yield a clear composition (composition solids:15.7%; SiO₂ wt % based on total dry solids: 10%).

Example 17

To the composition of Example 15 (20 g) was added “WXF/2% MPTSFormulation” (5.5 g) to yield a clear composition (composition solids:12.9%; SiO₂ wt % based on total dry solids: 20%).

Example 18

To colloidal silica (Ludox™ HS-40 hydrosol available from Du Pont, 7.5g, 3.0 g solids) was added concentrated ammonia (1.5 g) and water (16.0g), followed by addition of “WXF/2% MPTS Formulation” (35.0 g, 7.0 gsolids) with stirring. The resulting composition was translucent(composition solids: 16.7%; SiO₂ wt % based on total dry solids: 30%).

Example 19

To the composition of Example 18 (20 g) was added “WXF/2% MPTSFormulation” (16.7 g) to yield a translucent composition (compositionsolids: 18.2%; SiO₂ wt % based on total dry solids: 15%).

Example 20

To colloidal silica (Ludox™ TM-50 hydrosol available from Du Pont, 8.0g, 4.0 g solids) was added concentrated ammonia (1.5 g) and water (20.5g), followed by addition of “WXF/2% MPTS Formulation” (30.0 g, 6.0 gsolids) with stirring. The resulting composition was translucent(composition solids: 16.7%; SiO₂ wt % based on total dry solids: 40%).

Example 21

To the composition of Example 20 (20 g) was added “WXF/2% MPTSFormulation” (16.7 g) to yield a translucent composition (compositionsolids: 18.2%; SiO₂ wt % based on total dry solids: 20%).

Example 22

To colloidal silica (Nalco™ 2329 hydrosol available from Nalco,Naperville, Ill., 15.0 g, 6.0 g solids) was added concentrated ammonia(2.0 g) and water (23.0 g), followed by addition of “WXF/2% MPTSFormulation” (20.0 g, 4.0 g solids) with stirring. The resultingcomposition was milky (composition solids: 16.7%; SiO₂ wt % based ontotal dry solids: 60%).

Example 23

To the composition of Example 22 (10 g) was added “WXF/2% MPTSFormulation” (11.8 g) to yield a milky composition (composition solids:18.5%; SiO₂ wt % based on total dry solids: 25%).

Example 24

To the composition of Example 22 (25 g) was added “WXF/2% MPTSFormulation” (10.5 g) to yield a milky composition (composition solids:17.7%; SiO2 Wt% based on total dry solids: 40%).

TABLE 3 SiO₂ Hydrosol SiO₂ SiO₂ Surface (particle size, Weight % Area(based (nm); specific (based on on total surface area, Weight totalsolids; Pen Sample (m²/g)) % F solids) (m²/g)) Test Comparative — 22.20.0 — 3 Example 7 15 Ludox ™ SM- 15.5 30.0 108  0 30 (7; 360) 16 Ludox ™SM- 20.0 10.0 36 3 30 (7; 360) 17 Ludox ™ SM- 17.8 20.0 72 2 30 (7; 360)18 Ludox ™ HS- 18.9 15.0 36 3 40 (12; 240) 19 Ludox ™ HS- 15.5 30.0 72 040 (12; 240) 20 Ludox ™ TM- 17.8 20.0 28 3 50 (22; 140) 21 Ludox ™ TM-13.3 40.0 48 0 50 (22; 140) 22 Nalco ™ 2329 16.7 25.0 10 3 (75; 40) 23Nalco ™ 2329 13.3 40.0 16 3 (75; 40) 24 Nalco ™ 2329 8.9 60.0 24 0 (75;40)

The data in Table 3 indicates that in order to maintain acceptably lowsurface energy properties, colloidal silica can generally not be addedto the flourochemical compositions in excessive amounts, as measured bythe silica weight percent and/or the total surface area of added silica.The surface energy properties can also be influenced by the weightpercent flourine in the compositions. It has been found that the bestmeasure of the low surface energy properties is generally the pen test.

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of the invention.

What is claimed is:
 1. A cured composition that is prepared by curing awater-based composition comprising an aqueous solution, emulsion, ordispersion of (a) a water-soluble or water-dispersible polymer oroligomer having at least one anionic moiety which is capable of reactingwith an oxazoline or oxazine moiety: (b) a water-soluble orwater-dispersible polymer or oligomer having at least one oxazoline oroxazine moiety; and (c) from about 15 to about 40 weight percentcolloidal silica having an average particle diameter in the range offrom about 20 to about 75 nanometers, said weight percent being based onthe total weight of colloidal silica and polymer solids; at least one ofsaid components (a) and (b) further comprising at least onefluoroaliphatic moiety; and said composition having a fluorine contentof at least about 10 weight percent.
 2. The cured composition of claim 1wherein said cured composition exhibits a non-zero pen test value. 3.The cured composition of claim 1 comprising a crosslinked polymercontaining at least one amide-ester crosslink moiety, derived from thereaction of carboxyl groups with oxazoline or oxazine moieties, andhaving colloidal silica integrated therein.
 4. A coated articlecomprising the cured composition of claim
 1. 5. The cured composition ofclaim 1 wherein said polymer or oligomer having at least one anionicmoiety further comprises at least one fluoroaliphatic moiety.
 6. Thecured composition of claim 1 wherein said polymer or oligomer having atleast one oxazoline or oxazine moiety further comprises at least onefluoroaliphatic moiety.
 7. The cured composition of claim wherein saidanionic moiety is a carboxylic acid or carboxylate group.
 8. The curedcomposition of claim 1 wherein said polymer or oligomer having at leastone anionic moiety comprises interpolymerized units derived from atleast one fluoroaliphatic radical-containing acrylate and at least onecarboxy-containing monomer.
 9. The cured composition of claim 1 whereinsaid polymer or oligomer having at least one oxazoline or oxazine moietycomprises polymerized units derived from 2-isopropenyl-2-oxazoline. 10.The cured composition of claim 1 wherein said polymer or oligomer havingat least one oxazoline or oxazine moiety comprises interpolymerizedunits derived from at least one aliphatic or fluoroaliphaticradical-containing acrylate and 2-isopropenyl-2-oxazoline.